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Title: Operando Observations and First-Principles Calculations of Reduced Lithium Insertion in Au-Coated LiMn 2O 4

Abstract

The deposition of protective coatings on the spinel LiMn 2O 4 (LMO) lithium–ion battery cathode is effective in reducing Mn dissolution from the electrode surface. Although protective coatings positively affect LMO cycle life, much remains to be understood regarding the interface formed between these coatings and LMO. Using operando powder X–ray diffraction with Rietveld refinement, it is shown that, in comparison to bare LMO, the lattice parameter of a model Au–coated LMO cathode is significantly reduced upon relithiation. Less charge passes through Au–coated LMO in comparison to bare LMO, suggesting that the reduced lattice parameter is associated with decreased Li + solubility in the Au–coated LMO. Density functional theory calculations show that a more Li +–deficient near–surface is thermodynamically favorable in the presence of the Au coating, which may further stabilize these cathodes through suppressing formation of the Jahn–Teller distorted Li 2Mn 2O 4 phase at the surface. Electronic structure and chemical bonding analyses show enhanced hybridization between Au and LMO for delithiated surfaces leading to partial oxidation of Au upon delithiation. Furthermore, this study suggests that, in addition to transition metal dissolution from electrode surfaces, protective coating design must also balance potential energy effects induced by charge transfer atmore » the electrode–coating interface.« less

Authors:
 [1];  [2];  [2];  [3];  [1];  [1];  [3];  [3];  [3];  [3];  [2]; ORCiD logo [4]
  1. Univ. of Illinois, Urbana-Champaign IL (United States)
  2. Purdue Univ., West Lafayette, IN (United States)
  3. Argonne National Lab. (ANL), Lemont, IL (United States)
  4. Univ. of Illinois, Urbana-Champaign, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC), Energy Frontier Research Center. Center for Electrochemical Energy Science (CEES); USDOE
OSTI Identifier:
1524583
Alternate Identifier(s):
OSTI ID: 1491060
Grant/Contract Number:  
AC02-06CH11357; AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Advanced Materials Interfaces
Additional Journal Information:
Journal Volume: 6; Journal Issue: 4; Journal ID: ISSN 2196-7350
Publisher:
Wiley-VCH
Country of Publication:
United States
Language:
English
Subject:
density functional theory; lithium manganese oxide; lithium-ion batteries; operanso X-ray diffraction; protective coatings

Citation Formats

Bassett, Kimberly L., Warburton, Robert E., Deshpande, Siddharth, Fister, Timothy T., Ta, Kim, Esbenshade, Jennifer L., Kinaci, Alper, Chan, Maria K. Y., Wiaderek, Kamila M., Chapman, Karena W., Greeley, Jeffrey P., and Gewirth, Andrew A. Operando Observations and First-Principles Calculations of Reduced Lithium Insertion in Au-Coated LiMn2O4. United States: N. p., 2019. Web. doi:10.1002/admi.201801923.
Bassett, Kimberly L., Warburton, Robert E., Deshpande, Siddharth, Fister, Timothy T., Ta, Kim, Esbenshade, Jennifer L., Kinaci, Alper, Chan, Maria K. Y., Wiaderek, Kamila M., Chapman, Karena W., Greeley, Jeffrey P., & Gewirth, Andrew A. Operando Observations and First-Principles Calculations of Reduced Lithium Insertion in Au-Coated LiMn2O4. United States. doi:10.1002/admi.201801923.
Bassett, Kimberly L., Warburton, Robert E., Deshpande, Siddharth, Fister, Timothy T., Ta, Kim, Esbenshade, Jennifer L., Kinaci, Alper, Chan, Maria K. Y., Wiaderek, Kamila M., Chapman, Karena W., Greeley, Jeffrey P., and Gewirth, Andrew A. Wed . "Operando Observations and First-Principles Calculations of Reduced Lithium Insertion in Au-Coated LiMn2O4". United States. doi:10.1002/admi.201801923.
@article{osti_1524583,
title = {Operando Observations and First-Principles Calculations of Reduced Lithium Insertion in Au-Coated LiMn2O4},
author = {Bassett, Kimberly L. and Warburton, Robert E. and Deshpande, Siddharth and Fister, Timothy T. and Ta, Kim and Esbenshade, Jennifer L. and Kinaci, Alper and Chan, Maria K. Y. and Wiaderek, Kamila M. and Chapman, Karena W. and Greeley, Jeffrey P. and Gewirth, Andrew A.},
abstractNote = {The deposition of protective coatings on the spinel LiMn2O4 (LMO) lithium–ion battery cathode is effective in reducing Mn dissolution from the electrode surface. Although protective coatings positively affect LMO cycle life, much remains to be understood regarding the interface formed between these coatings and LMO. Using operando powder X–ray diffraction with Rietveld refinement, it is shown that, in comparison to bare LMO, the lattice parameter of a model Au–coated LMO cathode is significantly reduced upon relithiation. Less charge passes through Au–coated LMO in comparison to bare LMO, suggesting that the reduced lattice parameter is associated with decreased Li+ solubility in the Au–coated LMO. Density functional theory calculations show that a more Li+–deficient near–surface is thermodynamically favorable in the presence of the Au coating, which may further stabilize these cathodes through suppressing formation of the Jahn–Teller distorted Li2Mn2O4 phase at the surface. Electronic structure and chemical bonding analyses show enhanced hybridization between Au and LMO for delithiated surfaces leading to partial oxidation of Au upon delithiation. Furthermore, this study suggests that, in addition to transition metal dissolution from electrode surfaces, protective coating design must also balance potential energy effects induced by charge transfer at the electrode–coating interface.},
doi = {10.1002/admi.201801923},
journal = {Advanced Materials Interfaces},
issn = {2196-7350},
number = 4,
volume = 6,
place = {United States},
year = {2019},
month = {1}
}

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